EP3390676B1 - Leaching aids and methods of using leaching aids - Google Patents

Leaching aids and methods of using leaching aids Download PDF

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Publication number
EP3390676B1
EP3390676B1 EP16873550.4A EP16873550A EP3390676B1 EP 3390676 B1 EP3390676 B1 EP 3390676B1 EP 16873550 A EP16873550 A EP 16873550A EP 3390676 B1 EP3390676 B1 EP 3390676B1
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Prior art keywords
solution
ppm
leaching
compound
metal
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English (en)
French (fr)
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EP3390676A4 (en
EP3390676A1 (en
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Jack Bender
Nathan C. EMMERICH
Russell Vincent BREWER
Lauren Michelle HIGHT
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/1641—Leaching with acyclic or carbocyclic agents of a single type with ketones or aldehydes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the disclosure relates generally to the field of extractive metallurgy.
  • the disclosure relates to leaching aids, for example, when present in a leaching solution, and methods of using the leaching aids.
  • the leaching aids can include one or a combination of components.
  • the method of using the leaching aids can include a process of recovering metal from ore, for example, a process involving heap leaching, solvent extraction and electrowinning.
  • Copper, copper alloys and several other valuable metals have been in use for thousands of years. Because of the importance of such metals, numerous entities have and continue to research ways to increase the efficiency and productivity of procurement methods. It is critical for mines to maximize efficiency when extracting metals from ore. Copper-containing ores are typically classified into two categories - oxidic and sulfidic ores. Oxidic ores (e.g., cuprite, malachite, and azurite) are found near the surface as they are oxidation products of the deeper secondary and primary sulfidic ores (e.g., chalcopyrite, bornite, and chalcocite).
  • Oxidic ores e.g., cuprite, malachite, and azurite
  • secondary and primary sulfidic ores e.g., chalcopyrite, bornite, and chalcocite
  • mines Due to the chemical nature of copper oxides and secondary sulfides, mines typically treat the ore with hydrometallurgical processes - i.e., heap leaching, solvent extraction, and electrowinning. Approximately 20% of the world's annual copper production is obtained through hydrometallurgical processes.
  • Leaching is typically accomplished by applying a lixiviant to a collection of ore.
  • the most common lixiviant used in the mining industry is sulfuric acid (“H 2 SO 4 ") because it provides efficient and cost effective liberation of the metal from the ore.
  • the leaching process can be a heap, dump, percolation or agitation leaching process.
  • the intrinsic principles of leaching are the same: "1. [The process]...must dissolve the ore minerals rapidly enough to make commercial extraction possible[.]...[The process] should show chemical inertness toward gangue minerals...
  • Heap leaching is a common method of leaching in hydrometallurgical processes; however, this method has disadvantages.
  • metal-containing material When metal-containing material is piled into a heap and sprayed with a solution of dilute acid, significant time is required for the solution to percolate down through the heap before it can be collected and supplied to subsequent operations.
  • the extraction process can require several days to months.
  • Further issues arise when the fine particles in the heap accumulate between larger pieces of ore and decrease the speed of downward flow of the leaching solution or block the flow altogether. This results in channeling of the leachate (i.e., where the solution follows the path of least resistance through the heap), less contact with the packed fines, and a lower than expected concentration of metal in the resulting pregnant leaching solution ("PLS").
  • PLS pregnant leaching solution
  • the ore can be agglomerated before applying the leaching solution.
  • agglomerating agents can be incorporated into the leaching solution and/or raffinate. Agglomerating agents function as binding agents for the smaller fines to the larger ore particles. This binding allows for more uniform percolation of the leaching solution through the heap.
  • Such agglomerating agents can include strong acid and water combinations, anionic acrylamides, copolymers of acrylamide and acrylic acid, hydroxamated polymers, polyvinyl alcohols, ammonium cation and acrylamide-derived copolymers, and copolymers including combinations of poly (acrylamide), poly(acrylamide/sodium acrylate), poly(diallyldimethylammonium chloride), poly(acrylamide/diallyldimethylammonium chloride) and poly(diallyldimethylammonium chloride/vinyltrimethoxysilane) groups.
  • agglomerating agents are their limited ability to withstand acidic conditions, for example, from a sulfuric acid leaching solution. Breakdown of the agglomerating agents results in subsequent breakdown of the agglomerated particles. This quickly leads to the same issues as previously described, such as channeling and pooling within the heap. Channeling and pooling long have been a problem in heap leaching, and many have attempted to address such issues by introducing, for example, an antifoam, surfactant, or acid digestion agents.
  • the mining industry has not widely adopted, for example, organic polymer type agglomeration agents for heap leaching because of their incompatibility with processes (e.g., solvent extraction, electrowinning) downstream from the leaching operation and added cost.
  • US3266889 A discloses means of improving the bacterial leaching process so that when bacteria are placed in close proximity with sulfide minerals or sulfide ore samples, leaching starts more rapidly, continues at a higher rate, and increases the extraction of metal from the ore.
  • US3266889 A relates to the use of a group of chemicals, known as surface-active agents or surfactants, for accelerating bacterial leaching and for increasing the yield of metal -in solution.
  • US 6833479 B2 discloses antimisting agents for the control of mist generated above electrolyte solutions during the electrowinning, electroplating, and electroforming of metals present in the electrolyte solutions.
  • US 2013/0056357 A1 discloses acid mist mitigation agents for electrolyte solutions.
  • the leaching aids are compatible in all aspects of a process including heap leaching, solvent extraction and electrowinning.
  • the leaching solution comprises a lixiviant in an amount of 1g/l to 50 g/l, and one or more compound having formula (I): R((AO) n B) m ((AO) n H) p (I) wherein each AO group is, independently, an alkyleneoxy group selected from ethyleneoxy ("EO"), 1,2-propyleneoxy ("PO”), 1,2-butyleneoxy, and styryleneoxy; n is an integer from 0 to 40; m is an integer from 1 to the total number of OH hydrogens in the R group prior to alkoxylation; p is an integer such that the sum of m plus p equals the number of OH hydrogens in the R group prior to alkoxylation; B is H; R is a group selected from formula (II) to (VIII): R 1 C(CH 2 O) 3 (II) wherein R 1 is H, methyl, ethyl, or propyl; C(CH 2 O
  • the compound may be at a concentration of 5 to about 100 ppm, or about 5 ppm to about 50 ppm, or about 15 ppm to about 30 ppm, or about 25 ppm.
  • n can be 2 to 30, or 2 to 20, or 2 to 10.
  • the compound can include the following structure:
  • the lixiviant can be sulfuric acid, ammonia, or a mixture of ammonia and an ammonium salt (e.g., ammonium carbonate or ammonium sulfate) and the lixiviant can be at a concentration of, for example, about 1 g/L to about 25 g/L, about 1 g/L to about 15 g/L, about 1 g/L to about 10 g/L, about 5 g/L to about 25 g/L. In certain aspects, the lixiviant can be at a concentration of about 10 g/L, or about 5 g/L to about 50 g/L, or about 5 g/L to about 15 g/L of the leaching solution.
  • the compound can be at a total concentration of about 10 ppm to about 1000 ppm, or about 20 ppm to about 500 ppm or about 25 ppm to about 50 ppm, or about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm of the leaching solution.
  • Y can be a hydrogen, sodium, potassium or ammonium ion.
  • the leaching solution can further include a metal selected from a group consisting of copper, gold, silver, nickel, zinc, molybdenum, vanadium, uranium, and combinations thereof.
  • the lixiviant can be an alkaline cyanide solution where the ore is a gold and/or silver containing ore.
  • the leaching solution comprises a lixiviant in an amount of 1g/l to 50 g/l, and one or more compound having formula (IX): wherein R 3 is a C 1 to C 20 linear or branched alkyl group comprising zero or more substitutions with any of O, N, OH or R 4 and R 6 are each, independently, H, a C 1 to C 10 linear or branched alkyl group or an alcohol group, R 5 is a C 1 to C 10 linear or branched alkyl group; and wherein the compound is at a concentration of about 1 ppm to about 2000 ppm.
  • R 3 is a C 1 to C 20 linear or branched alkyl group comprising zero or more substitutions with any of O, N, OH or R 4 and R 6 are each, independently, H, a C 1 to C 10 linear or branched alkyl group or an alcohol group
  • R 5 is a C 1 to C 10 linear or branched alkyl group
  • the compound is at a concentration of about
  • R 3 can be a C 10 linear or branched alkyl group
  • R 4 and R 6 can be each, independently, a C 1 to C 4 alkyl group and/or R 5 can be a C 1 to C 4 alkyl group.
  • the compound can have the structure:
  • R 3 can have at least one substitution and/or R 4 and R 6 are each, independently, H or an alcohol group.
  • the compound can have the structure: wherein R 7 is a C 1 to C 20 linear or branched alkyl group comprising zero or more substitutions with any of O, N, OH or
  • the lixiviant in the leaching solution can be sulfuric acid or ammonia.
  • the lixiviant can be sulfuric acid at a concentration of, for example, about 1 g/L to about 25 g/L, about 1 g/L to about 15 g/L, about 1 g/L to about 10 g/L, about 5 g/L to about 25 g/L. In certain aspects, the lixiviant can be at a concentration of about 10 g/L, or about 5 g/L to about 50 g/L, or about 5 g/L to about 15 g/L of the leaching solution.
  • the compound can be at a total concentration of about 10 ppm to about 1000 ppm, or about 20 ppm to about 500 ppm, or about 25 ppm to about 50 ppm, or about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm, or about 15 ppm to about 30 ppm or about 25 ppm.
  • the leaching solution can further include a metal selected from a group consisting of copper, gold, silver, nickel, zinc, molybdenum, vanadium, uranium, and combinations thereof.
  • the leaching solution can include a lixiviant; and one or more compound having a formula (X), (XI), (XII) or (XIII) as follows:
  • the leaching solution can include a lixiviant; and one or more of the compounds described above.
  • the disclosure relates to a method of leaching a metal from an ore, the method comprising: contacting the ore comprising the metal with any of the leaching solutions described above.
  • Contacting the ore can include variety of leaching techniques including heap leaching, dump leaching, vat leaching or agitation leaching.
  • the metal can be selected from a group consisting of copper, gold, silver, nickel, zinc, molybdenum, vanadium, uranium, and combinations thereof.
  • the metal comprises copper.
  • the ore is agglomerated or not agglomerated.
  • the disclosure relates to a method of recovering a metal from an ore, comprising: contacting the ore comprising the metal with any of the leaching solutions described above to form a pregnant leaching solution; and recovering the metal from the pregnant leaching solution.
  • the recovering of the metal can include a solvent extraction process.
  • the compound in the leaching solution can be compatible with the solvent extraction process.
  • Recovering the metal can include an electrowinning process where the compound in the leaching solution is compatible with the electrowinning process.
  • the metal can be selected from a group consisting of copper, gold, silver, nickel, zinc, molybdenum, vanadium, uranium, and combinations thereof.
  • the metal is copper and the lixiviant is sulfuric acid or the metal is gold and/or silver and the lixiviant is an alkaline cyanide solution.
  • Example aspects are described herein in the context of leaching aids in leaching solutions and methods of using the leaching aids. Those of ordinary skill in the art will recognize that the following description is illustrative only and is not intended to be in any way limiting. Other aspects will readily suggest themselves to those of ordinary skill in the art having the benefit of this disclosure. Reference will now be made in detail to implementations of the example aspects as illustrated in the accompanying drawings. The same reference indicators will be used to the extent possible throughout the drawings and the following description to refer to the same or like items.
  • the disclosure is directed to leaching solutions including leaching aids for improving the rate of recovery and/or the total recovery of metals from non-agglomerated or agglomerated ore.
  • leaching solutions are compatible with various mining processes including solvent extraction and electrowinning.
  • leaching solutions can comprise leaching aids which include, but are not limited to, one or any combination of the following classes of compounds:
  • the leaching solutions can include a lixiviant and one or more leaching aid having formula (I) as follows: R((AO) n B) m ((AO) n H) p (I) where each AO group is, independently, an alkyleneoxy group selected from ethyleneoxy ("EO"), 1,2-propyleneoxy ("PO”), 1,2-butyleneoxy, and styryleneoxy; n is an integer from 0 to 40; m is an integer from 1 to the total number of OH hydrogens in the R group prior to alkoxylation; p is an integer such that the sum of m plus p equals the number of OH hydrogens in the R group prior to alkoxylation; B is H, SO 3 Y, (CH 2 ) q SO 3 Y, CH 2 CHOHCH 2 SO 3 Y, or CH 2 CH(CH 3 )OSO 3 Y, wherein q is an integer from 2 to 4 and Y is a cation; R((AO) n B) m (
  • n can be 2 to 30, or 2 to 20, or 2 to 10
  • B can be Hydrogen and R can have formula (II).
  • the leaching solution can include a leaching aid comprising a distribution of compounds including the following structure, which leaching aid may be referred to herein as "TMP-7(EO)":
  • TMP-EO x,y,z ethylene oxide
  • the resulting mixture of compounds includes one of the above TMP-7(EO) structure.
  • the alkoxylation is preferably catalyzed by strong bases which are added in the form of an alkali metal alcoholate, alkali metal hydroxide or alkaline earth metal hydroxide, in an amount of about 0.1% to about 1% by weight, based on the amount of the alkanol RZiOH (cf. G. Gee et al., J. Chem. Soc. (1961), page 1345 ; B. Wojtech, Makromol. Chem. 66, (1966 ), page 180).
  • Lewis acids such as, for example, AlCl 3 or BF 3 dietherate, BF 3 , BF 3 H 3 PO 4 ,
  • Double metal cyanide (DMC) compounds are also suitable as the catalyst.
  • DMC compounds suitable as a catalyst are described, for example, in WO 99/16775 and DE-A-101 17 273 .
  • Particularly suitable catalysts for the alkoxylation are double metal cyanide compounds of the general formula (A): M 1 a [M 2 (CN) b (A) c ] d . h (H 2 O) .e L .k P (A) where
  • the organic additive P can include: polyether, polyester, polycarbonates, polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether, polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-coacrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethylcellulose, polyacetates, ionic surface-active and interface-active compounds, gallic acid
  • These catalysts may be crystalline or amorphous. Where k is zero, crystalline double metal cyanide compounds are preferred. Where k is greater than zero, crystalline, semicrystalline and substantially amorphous catalysts are preferred.
  • Preferred embodiment catalysts can be of the formula (A) in which k is greater than zero.
  • the preferred catalyst then comprises at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.
  • k is zero, e is optionally also zero and X is exclusively a carboxylate, preferably for mate, acetate and propionate.
  • Such catalysts are described in WO 99/ 1 6775 .
  • crystalline double metal cyanide catalysts are preferred.
  • Double metal cyanide catalysts as described in WO 00/74845 which are crystalline or lamellar, are furthermore preferred.
  • the preparation of the modified catalysts is effected by combining a metal salt solution with a cyanometallate solution which may optionally comprise both an organic ligand L and an organic additive P.
  • the organic ligand and optionally the organic additive are then added.
  • an inactive double metal cyanide phase is first prepared and this is then converted into an active double metal cyanide phase by recrystallization, as described in WO 01/64772 .
  • f, e and k are not zero.
  • double metal cyanide catalysts which comprise a water-miscible organic ligand (in general in amounts of from 0.5 to 30% by weight) and an organic additive (in general in amounts of from 5 to 80% by weight), as described in WO 98/06312 .
  • the catalysts can be prepared either with vigorous stirring (24,000 rpm using a Turrax) or with stirring, as described in US. Pat. No. 5,158,922 .
  • catalysts for the alkoxylation are double metal cyanide compounds which comprise zinc, cobalt or iron or two thereof.
  • Prussian Blue is particularly suitable.
  • Crystalline DMC compounds are preferably used.
  • a crystalline DMC compound of the Zn 4 Co type which comprises zinc acetate as a further metal salt component, is used as the catalyst.
  • Such compounds are crystallized with a monoclinic structure and have a lamellar habit.
  • Such compounds are described, for example, in WO 00/74845 or WO 01/64772 .
  • DMC compounds suitable as a catalyst can be prepared in principle by all methods known to the person skilled in the art.
  • the DMC compounds can be prepared by direct precipitation, by the incipient Wetness method or by preparation of a precursor phase and subsequent recrystallization.
  • the DMC compounds can be used as a powder, paste or suspension or can be shaped to give a molding, introduced into moldings, foams or the like or applied to moldings, foams or the like.
  • the catalyst concentration used for the alkoxylation is typically less than 2000 ppm (i.e. mg of catalyst per kg of product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm.
  • the addition reaction can be carried out at temperatures of about 90°C to about 2400°C., preferably from 120°C to 1800°C., in a closed vessel.
  • the alkylene oxide or the mixture of different alkylene oxides is added to the mixture of alkanol mixture according to the invention and alkali under the vapor pressure of the alkylene oxide mixture which prevails at the chosen reaction temperature.
  • the alkylene oxide can be diluted with up to about 30% to 60% of an inert gas. This provides additional safety with regard to prevention of explosive polyaddition of the alkylene oxide.
  • polyether chains in which the different alkylene oxide building blocks are virtually randomly distributed are formed. Variations in the distribution of the building blocks along the polyether chain are the result of different reaction rates of the components and can also be achieved randomly by continuous feeding of an alkylene oxide mixture of program-controlled composition. If the different alkylene oxides are reacted in succession, polyether chains having a block-like distribution of alkylene oxide building blocks are obtained.
  • Alkoxylate mixtures of the general formula (B) (below) can be obtained by reacting alcohols of the general formula C 5 H 11 CH(C 3 H 7 )CH 2 OH with propylene oxide/ethylene oxide in the abovementioned sequence under alkoxylation conditions.
  • R 1 -O-(CH 2 -O-CHR 5 -O-) r (CH 2- CH 2 -O-) n CH 2 -CHR 6 -O-) x (CH 2 -CHR 2 -O-) m H (B) where
  • Suitable alkoxylation conditions are described above and in Nikolaus Schönfeldt, Grenz inhabitassitule ⁇ thylenoxid-Addukte,ticianliche Verlagsgesellschaft mbH Stuttgart 1984.
  • the alkoxylation is carried out in the presence of basic catalysts, such as KOH, in the absence of a solvent.
  • the alkoxylation can, however, also be carried out with the concomitant use of a solvent.
  • a polymerization of the alkylene oxide is initiated in which a random distribution of homologs inevitably occurs, the mean value of which is specified here with p, n, m and q.
  • the mixture comprises the following compound:
  • the leaching solution can include a leaching aid having formula (IX) as follows: where R 3 is a C 1 to C 20 linear or branched alkyl group comprising zero or more substitutions with any of O, N, OH or R 4 and R 6 are each, independently, H, a C 1 to C 10 linear or branched alkyl group or an alcohol group, and R 5 is a C 1 to C 10 linear or branched alkyl group.
  • the term "alcohol group” means a C 1 to C x linear or branched alkyl group having an -OH functionality where x is an integer, for example, x can be from 2 to 10 or from 2 to 20.
  • R 3 can be a C 10 linear or branched alkyl group and R 4 , R 5 and R 6 can be, independently, a C 1 to C 3 alkyl group.
  • the leaching solution can include a leaching aid having the following structure, which compound may be referred to herein as "MC1000":
  • R 3 can include at least one substitution
  • R 4 and R 6 can be, independently, H or an alcohol group.
  • the leaching solution can include a leaching aid having the following structure: where R 7 is a C 1 to C 20 linear or branched alkyl group comprising zero or more substitutions with any of O, N, OH or
  • the leaching solution can include a leaching aid such as an alkyl or alkyl ether sulfate having formula (X) or (XI) as follows: where s and t are each, independently, an integer from 0 to 10 and R 8 and R 9 are each, independently, a C 1 to C 20 linear or branched alkyl group.
  • a leaching aid such as an alkyl or alkyl ether sulfate having formula (X) or (XI) as follows: where s and t are each, independently, an integer from 0 to 10 and R 8 and R 9 are each, independently, a C 1 to C 20 linear or branched alkyl group.
  • the leaching solution can include a leaching aid having formula (XII) as follows: R 10 CH 2 OC(O)C(SO 3 - )CH 2 C(O)OCH 2 R 11 Na + (XII), where R 10 and R 11 are each, independently, a C 1 to C 6 linear or branched alkyl group.
  • a leaching aid having formula (XII) as follows: R 10 CH 2 OC(O)C(SO 3 - )CH 2 C(O)OCH 2 R 11 Na + (XII), where R 10 and R 11 are each, independently, a C 1 to C 6 linear or branched alkyl group.
  • the leaching solution can include, in various example aspects, an acetylenic diol as a leaching aid having the following formula (XIII): where R 12 is a C 1 to C 6 linear or branched alkyl group.
  • the leaching solution can include, an amphoacetate as a leaching aid having the following formula (XIV): wherein R 13 is a C 2 to C 20 linear or branched alkyl group.
  • the one or more leaching aids can be added to any leaching solution for any type of leaching technique where an aqueous solution is used to remove metal from an ore.
  • the one or more leaching aids can be added to the leaching solution at a total concentration of about 1 parts per million ("ppm") to about 2000 ppm, or about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm, or about 15 ppm to about 30 ppm, or about 10 ppm to about 1000 ppm, or about 20 ppm to about 500 ppm, or about 10 ppm to 100 ppm, or about 10 ppm to about 50 ppm, or about 25 ppm to about 50 ppm of the leaching solution, or about 50 ppm to less than the critical micelle concentration of the leaching aid.
  • ppm parts per million
  • Critical micelle values can be, for example, about 100 ppm to about 1000 ppm.
  • the leaching solution can include a leaching aid of formula (I) or (IX) at a total concentration of about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm, or about 15 ppm to about 30 ppm, or about 25 ppm, or about 10 ppm to about 100 ppm, or about 25 ppm to about 50 ppm of the leaching solution.
  • the leaching solution can include the TMP-7(EO) leaching aid or the MC1000 leaching aid at a total concentration of about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm, or about 15 ppm to about 30 ppm, or about 10 ppm to about 100 ppm, or about 25 ppm to about 50 ppm, or about 25 ppm of the leaching solution.
  • TMP-7(EO) leaching aid or the MC1000 leaching aid at a total concentration of about 5 ppm to about 50 ppm, or about 5 ppm to about 100 ppm, or about 15 ppm to about 30 ppm, or about 10 ppm to about 100 ppm, or about 25 ppm to about 50 ppm, or about 25 ppm of the leaching solution.
  • a leaching solution can include a lixiviant and one or more leaching aid of formulas (I) and (IX) - (XIV) described above.
  • the leaching solution can include both the TMP-7(EO) leaching aid and the MC1000 leaching aid.
  • the lixiviant can be any suitable acid or base for leaching metal values from an ore.
  • the lixiviant can be sulfuric acid, ammonia, ammonium carbonate, ammonium sulfate, ammonium chloride or cyanide solutions.
  • the lixiviant can be, for example, sulfuric acid or ammonia.
  • the lixiviant can be, for example, an alkaline cyanide solution.
  • the metal/metalloid values can be in ionic form and/or in elementary form.
  • the metals/metalloids can be one or more of copper, gold, silver, nickel, zinc, molybdenum, vanadium, uranium, and combinations thereof.
  • the metal can be copper.
  • ore leaching aids described herein can reduce the surface tension of the leaching solution and provide better wetting of the ore during heap leaching whether or not the ore is agglomerated. Additionally, this reduction in surface tension can prevent or reduce capillary action in the microscopic crevices of the ore.
  • the addition of surface active agents as leaching aids to the leaching solution can liberate the metal-containing solution from the crevices allowing fresh solution to penetrate into the crevices.
  • the capillary action can be reduced to about 80%, or about 70% or about 60% less than that of water alone through the addition of one or more of the leaching aids. This decrease in capillary action liberates the leaching solution from the crevice, which ultimately increases the rate of recovery and/or the total recovery of metal from the ore.
  • the leaching aids are compatible with several processes and process conditions, including, but not limited to, agglomeration, leaching, solvent extraction, and electrowinning.
  • the one or more leaching aids can have no or a limited impact on other processes, such that they are compatible with downstream processes after the one or more leaching aids have been used to recover the metal during leaching.
  • solvent extraction is a carefully orchestrated balance of various metal and acid concentrations.
  • the foundation of many forms of solvent extraction are built around the hydrogen ion cycle: Vladimir S. Kislik, Solvent Extraction: Classical and Novel Approaches, p.191.
  • the delicate chemical balance that is inherent to all solvent extraction operations can be negatively affected by the slightest interloper.
  • all of the processes are interconnected and form a symbiotic relationship as shown in FIG. 2 .
  • an additive is meant to amplify one part of the process (e.g., copper leaching) it could easily disrupt another segment (e.g., copper extraction) due to incompatible chemistry.
  • Issues such as these can include: the formation of emulsions, entrainment, introduction of impurities into the tankhouse, manipulation of extraction and/or strip kinetics, degradation or staining of the reagent, or nullification of a particular step of the process.
  • the leaching aids are compatible with leaching, extraction, stripping and electrowinning operations and do not result in the above mentioned issues.
  • the leaching aid can be added to a lixiviant solution that is passed through an ore during an extraction process.
  • the ore may be subjected to an agglomeration process prior to leaching with the lixiviant solution.
  • the leaching aid can be added to water and the lixiviant (e.g., sulfuric acid) used in an agglomeration process with no further addition of the leaching aid to the lixiviant solution circulated through the ore to leach the metal (e.g., copper).
  • the leaching aid can be added to a portion of the lixiviant solution with or without the addition of additional acid for use as an agglomeration aid followed by passing lixiviant through the ore with or without the leaching aid.
  • the one or more leaching aids used for improving the rate of recovery and/or total recovery of metals from ore, where the ore may or may not have been agglomerated, and which are compatible with numerous mining processes, can have various general characteristics.
  • the leaching aids can be anionic, cationic, nonionic or amphoteric surfactants or mixtures thereof.
  • the leaching aids can be low-foaming surfactants.
  • Suitable cationic surfactants include tetraalkylammonium salts, imidazolinium salts, amine oxides or mixtures thereof.
  • tetraalkylammonium salts include C 8 - to C 16 -dialkyldimethylannnonium salts, dialkoxydimethylammonium salts, imidazolinium salts having a long-chain alkyl radical, or mixtures thereof.
  • amphoteric surfactants can include, as monomer units, derivatives of diallylamine, in particular, dimethyldiallylammonium salt and/or methacrylamidopropyl(trimethyl)ammonium salt, for example, in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrogen sulfate, ethylsulfate, methylsulfate, mesylate, tosylate, formate or acetate, and/or in combination with ethyleneically unsaturated carboxylic acid monomer units.
  • Suitable non-ionic surfactants can include alcohol alkoxylates (e.g., alkoxylated polyols), alkylphenol alkoxylates, alkylpolyglucosides, N-alkylpolyglucosides, N-alkylglucamides, fatty acid alkoxylates, fatty acid polyglycol esters, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, N-alkoxypolyhydroxyfatty acid amides, N-aryloxypolyhydroxy-fatty acid amides, block copolymers of ethylene oxide, propylene oxide and/or butylene oxide, polyisobutene alkoxylates, polyisobutene/maleic anhydride derivatives, fatty acid glycerides, sorbitan esters, polyhydroxy-fatty acid derivatives, polyalkoxy-fatty acid derivatives, bisglycerides, or mixtures thereof.
  • Suitable anionic surfactants can include fatty alcohol sulfates, sulfated alkoxylated alcohols, alkanesulfonates, N-acyl sarcosinates, alkylbenzenesulfonates, olefin sulfonates and olefin disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkylglyceryl sulfonates, fatty acid glyceryl ester sulfonates, alkylphenol polyglycol ether sulfates, paraffinsulfonates, alkyl phosphates, acyl isothionates, acyl taurates, acylmethyl taurates, alkylsuccinic acids, alkenylsuccinic acids or the monoesters or monoamides thereof, alkylsulfosuccinic acids or the amides thereof, mono- and diesters of
  • leaching aids include high water solubility in the aqueous leaching solution to avoid extraction into the organic phase during solvent extraction.
  • Other characteristics of the leaching aids include high critical micelle concentrations and stability at acidic pH.
  • the leaching aids can minimize foaming, and one or more surfactants can decrease the surface tension of the leaching solution.
  • the leaching aids also should have no or minimal impact on any other process related to extraction of the metal (e.g. leaching, solvent extraction, stripping and electrowinning including mixing, phase disengagement, extraction and strip kinetics, copper/iron selectivity or build up in the organic over time).
  • Suitable leaching aids furthermore, should be stable under the acidic conditions of the leaching solution (e.g., sulfuric acid) in an aqueous phase and should be biodegradable.
  • suitable leaching aids according to various example aspects of the disclosure can increase overall metal recovery (e.g., copper recovery) by at least 3%.
  • the suitable leaching aids according to the disclosure can increase overall metal recovery by about 0.5% to about 20% or about 1% to about 20%, or about 2% to about 20%, or about 5% to about 20%, or about 0.5% to about 10% or about 2% to about 10% or about 5% to about 10%.
  • the ore was precisely classified by SGS in Arlington, AZ.
  • the ore was a mostly copper oxide ore that had a P80 of 1.5" and a smallest fraction of -10 mesh.
  • the distribution of the column charge can be found in Table 1.
  • the copper concentration in the ore was 0.42% with 91.2% of the copper as acid soluble copper. Analysis of the ore was also verified by SGS in Arlington. Table 1 - Distribution of particle sizes of copper ore in leach tests.
  • the first set of column runs consisted of triplicates of Leaching Aid - A (i.e., the MC-1000 leaching aid referred to in this study as "LA-A”) at the following doses: LA-A (50 ppm dose), LA-A (25 ppm dose), and Leaching Aid - B (i.e., the TMP-7(EO) leaching aid referred to in this study as "LA-B”) at the following doses: LA-B (50 ppm dose), and LA-B (25 ppm dose).
  • LA-A Leaching Aid - A
  • LA-A 50 ppm dose
  • LA-B the TMP-7(EO) leaching aid referred to in this study as "LA-B”
  • LA-B the TMP-7(EO) leaching aid
  • Samples were collected daily for the first 30 days of the 60 day leaching trials. For each column, a sample was analyzed for pH, free acid, copper concentration by AA, surface tension, and oxidation potential (ORP). The lixiviant samples were also analyzed each day to ensure that there was no contamination or change in concentration of chemical species. The solution feed rates were measured every day and if any adjustments were needed, the appropriate changes were made.
  • the columns ran for 60 days.
  • the amount of copper leached was approximately 75% of the 92.1% of the copper in the ore that was acid soluble (from a bottle roll test).
  • copper leaching began to slow enough so that the trial was terminated.
  • Agglomeration was accomplished by mixing the various fractions in a cement mixer with 1.75 Kg of water and 1.52 Kg of sulfuric acid. The acid was calculated as 25% of the total acid consumption by ore. The agglomerated material was then transferred to columns for the leaching trials.
  • FIGs. 3A and 3B In order to show the efficiency of the leaching aid, the data in FIGs. 3A and 3B is plotted as the percent of copper leached in excess of the control.
  • the first ten days of leaching resulted in substantial increases in copper leaching for the LA-B (25 ppm) and the LA-A (50 ppm).
  • the LA-A 25 ppm had resulted in an average of 3.7% increase in copper leached from the ore.
  • the second set of column trials was essentially a repeat of the first set of column trials with a slight modification of the agglomeration procedure.
  • the lixiviant was not recirculated, but was added in a one pass system.
  • the LA-B 25 ppm
  • the LA-B had a substantial increase in copper leaching, approximately 5% more copper leached than the control.
  • the amount of copper leached in this trial was quite high, reaching the amount of copper leachable from the bottle test.
  • FIGs. 4A and 4B details the results of the second column trial.
  • a series of biological species relevant to mining applications were inoculated with the leaching aids and given relevant feed solutions; Acidophilium acidophilum (AA) - heterotroph, Acidiphilium cryptum (ACRP) - heterotroph, Acidithiobacillus ferrivorans (AFER) - iron and sulfur oxidizer (tested on iron), Acidithiobacillus ferrooxidans (AFEX) - iron oxidizer, Acidithiobacillus thiooxidans (ATEX) - sulfur oxidizer, Leptospirillum ferrooxidans (LFEX) - iron oxidizer, Acidithiobacillus caldus (ACALD) - sulfur oxidizer, Leptospirillum ferriphilum (LFER) - iron oxidizer, Ferroplasma acidiphilum ( FACID - archea iron oxidizer, Ferroplasma acidarmanus (FARM) - archea tested on iron oxidization, and Sulfobacillus acidiphilum (
  • a quantitative growth curve study was performed to determine the effect of the chemical additives on two organism groups, mesophiles and moderate thermophiles (28 and 42 degrees Celsius). These groups contained 3 sub-groups of metabolic function (heterotroph, iron oxidizers, sulfur oxidizers), primarily consisting of bacteria from several archaea.
  • the two leaching aids were labeled as "LA-A” (i.e., MC-1000) and "LA-B" (i.e., TMP-7(EO)) for the purposes of the biological testing.
  • the growth curves were scheduled to be completed within 45 days or when the cultures were deemed stabilized. Growth media utilized was UBM's base salt media UX2 with appropriate substrates and optimal initial pH values for each organism.
  • Each BASF chemistry was tested in triplicate and at three (3) different concentrations; 0.5x target concentration, target concentration, and 2x target concentration. Samples on triplicate cultures were taken every 3-5 days depending on the growth rate of the organisms, and cell counts were performed. Data was provided for LA-B exclusively.
  • the biological compatibility results for the LA-B leaching aid are shown in FIGs 5A-5K .
  • the two heterotrophs organisms that derive their nutrition from organic chemical species, there was no negative effect for the AA and for the ACRP there was an initial loss of population but there was a recovery which included a scavenging of organic from the death of organisms.
  • the sulfur oxidizers there was little impact of the leaching aid on cell colonies.
  • For the ACALD there was a slowing down of population growth at approximately 14 days; however, then the growth resumed.
  • Iron oxidizing species were either not affected at all or had some level of inhibition.
  • AFEX and LFEX were the two iron oxidizing bacteria that showed the most growth inhibition.
  • LA-A i.e., MC-1000
  • LA-B i.e., TMP-7(EO)
  • the testing regime included static kinetics testing, phase disengagement, and in some cases doping of solutions run in a dynamic circuit.
  • Table 2 details the application testing data for the chemical compatibility. These tests were conducted using the standard conditions outlined in the BASF method for quality control of oxime reagents entitled Standard Quality Control Test of LIX® Reagents (Doc. No. TG - TSH - 05, Rev. 4, Sep.
  • the samples were run in a continuous circuit for three days with PLS spiked with the leaching aid at twice the standard dosage, 50 ppm. The samples were then tested for phase disengagement and kinetics.
  • the extraction kinetics at 90s for the LA-B are a little lower, at 92.3%, than desired; however, the equilibrium extraction is equivalent to the control.
  • the strip kinetics were unaffected, suggesting that any contamination is not in the organic.
  • the phase disengagement for the LA-A doping was substantially affected, while the phase disengagement for the LA-B doping was unaffected. This data would suggest that the LA-B reagent is compatible with solvent extraction.
  • Copper cathode was plated using a rectifier and simple EW system.
  • the effect of adding a leaching aid was similar to that of a smoothing agent. This is due to the reduction of the surface tension and the attraction of the polar functional groups of the leaching aid to the high charge density of copper cathode dendrites. In no cases was there any negative impact from the leaching aid.
  • This example investigated a method for determining the impact of a leaching aid on the surface tension of a typical leaching solution.
  • a synthetic pregnant leaching solution (“PLS”) of 6 g/L copper and 2 g/L iron at a pH of about 2.0 was prepared in deionized (“DI”) water to form a quality control (“QC") feed.
  • DI deionized
  • QC quality control
  • mixtures of synthetic PLS having varying levels of Leach aid A (i.e., MC1000) or Leach Aid B (i.e., TMP-7(EO)) were prepared and the surface tension of each solution was measured.
  • the surface tension (dynes/cm) as a function of the concentration of the leaching aid (ppm) was plotted as shown in FIG. 6 . As shown, the surface tension decreased with increasing concentration of the leaching aid.
  • the circuits were configured to maintain 3 min retention times, with the ratio of organic to aqueous ("O:A") at about 2:1 (vol/vol) at room temperature with an aqueous flow rate of about 100 ml/h.
  • An aqueous recycle was used to maintain the O:A with continuous mixing of the organic solutions.
  • Example 5 showed that over the period of a week the results for the Leach Aid and the Blank were within experimental error. Additionally the results for the break times were also within experimental error. See Tables 3 and 4. Table 4 - Example 5 Results for EVD 91216 (i.e., MC1000) and the Blank EVD 91216 Blank delta (sec) Pre QC test Organic break 168 89 79 Aqueous Break 104 60 44 Extraction Organic break 60 69 -9 Aqueous Break 176 133 43 Strip Organic break 96 67 29 Aqueous Break 130 129 1
  • Organic solution was prepared with LIX984N and LIX860N-I (manufactured and sold by BASF) at a ratio of about 50:50 (v/v) at about 10 v/v% in ShellsolTM D70 manufactured by Shell Chemical LP.
  • This organic solution was twice contacted with a QC electrolyte at a ratio of about 1:1 (v/v) and about 500 ml of the resulting solution was then filtered through No. 1 PS paper to serve as an experimental control.
  • the remaining about 500ml of the organic solution was contacted with a QC electrolyte containing about 500 ppm of the MC1000 leaching aid.
  • a standard reagent QC test was then conducted for the two resulting organic solutions.
  • the organic solution that was contacted with the leaching aid was clay treated at a concentration of about 1 wt/v% and contacted with a synthetic QC feed (about 250 ml organic solution with about 250 ml aqueous solution) and the clay treated organic solution continuous break time was recorded.
  • Table 5 - Example 6 Results Leach Aid Blank Organic break 104 (C.T. 10sec) 52 Aqueous Break 117 120 SO 0.917 0.896 E30 4.022 4.65 E300 4.849 4.887 S30 1.063 1.08 S300 1.051 1.074 E300 Fe 0.0031 0.0024 E30 kinetics 82.9% 95.2% S30 kinetics 98.9% 99.4% Cu/Fe 1564 2036
  • Examples 5 and 6 showed that in the event of a significant overdose of the leaching aid, there could be a slight increase in phase disengagement and decrease in extraction kinetics which would be easily treatable by clay treatment ("C.T.”).
  • a blank leaching solution and a leaching solution containing the MC1000 leaching aid were prepared.
  • a carboy was filled with DI water to about the 20 L mark and about 202 g of concentrated sulfuric acid was added and mixed thoroughly.
  • a carboy was filled with DI water to about the 20 L mark and about 202 g of concentrated sulfuric acid and 2 g of leaching aid were added and mixed thoroughly.
  • FIG. 7 is a graph of an average of several column trials of a blank and a leaching aid.
  • This experiment explored a method for selecting one or more leaching aids as additives to a leaching solution.
  • the method approximates the results of 2 m (h) x 20 cm (d) laboratory scale columns.
  • FIG. 9A shows leaching curves from the first trial. Both TMP-7(EO) and MC1000 were tested at 50 ppm (high) and 25 ppm (low) concentrations. Each was run in triplicate (control in quadruplicate).
  • FIG. 9B shows a comparison of leaching results as a function of the control columns for Trial 1.
  • FIG. 9C shows a comparison of total copper recovered as a function of the control columns for Trial 2.
  • MC1000 was tested at 50 and 100 ppm
  • TMP-7(EO) was tested at 25 ppm
  • sulfated TMP-7(EO) was tested at 50 ppm.
  • TMP-7(EO) 25 ppm
  • MC1000 50 ppm
  • results for both compounds are reproducible throughout testing to date.

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